Speciation of heavy metals in cement-stabilized waste forms: A micro-spectroscopic study

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of industrial and radioactive waste in underground repositories. In this study, synchrotron based-techniques (micro X-ray spectroscopy (XAS) and micro X-ray fluorescence (XRF)) were used to investigate Co and Ni uptake by Hardened Cement Paste (HCP) with the aim of improving our understanding of the immobilization process of heavy metals in cement at the molecular level. For Ni and Co, XRF mapping revealed a highly heterogeneous element distribution as far as the concentration is concerned. The XAS studies further showed that Ni(II) forms predominantly layered double hydroxide (LDH) phases. In contrast to Ni, Co was found to be present in the oxidation states II and III. Co(II) is predominately incorporated into newly formed Co(II) hydroxide-like phases (Co(OH)2), Co-LDH or Co-phyllosilicates, whereas Co(III) tends to be incorporated into a Co(III)O(OH)-like phase or a Co-phyllomanganate.